JPH0674124B2 - Activation furnace and activation method - Google Patents
Activation furnace and activation methodInfo
- Publication number
- JPH0674124B2 JPH0674124B2 JP60296730A JP29673085A JPH0674124B2 JP H0674124 B2 JPH0674124 B2 JP H0674124B2 JP 60296730 A JP60296730 A JP 60296730A JP 29673085 A JP29673085 A JP 29673085A JP H0674124 B2 JPH0674124 B2 JP H0674124B2
- Authority
- JP
- Japan
- Prior art keywords
- activation
- furnace
- activated
- activated carbon
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電気二重層キャパシタ、電池などに用いる分
極性電極のための繊維状活性炭の製造方法、およびこれ
に用いる賦活炉に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing fibrous activated carbon for a polarizable electrode used in an electric double layer capacitor, a battery, etc., and an activation furnace used therefor.
従来の技術 活性炭繊維は従来（１）バッチ法，（２）連続法の２つ
の方法で賦活製造されている。すなわち第３図に示すよ
うに、布，不織布，フェルトなどの原料20を高温炉21の
中に保ち、不活性雰囲気22中で賦活ガス供給孔23から
水，炭酸ガスなどのガスを供給するのがバッチ法であ
る。24は賦活ガスタンク、25は炉の温度制御装置であ
る。この図ではヒータは省略してある。また第４図に示
すように、布，不織布，フェルトなどの原料30を炉31の
入口32から連続的に送り出し、賦活ガス供給孔33から賦
活ガスを供給し、原料を賦活し、炉の出口34から得られ
た活性炭繊維構成物を連続的に得る方法が連続法であ
る。35は賦活ガスタンク、36は炉の加熱用ヒータ、37は
原料30の送り出し装置、38は製品の捲き取り装置であ
る。Conventional Technology Activated carbon fibers are conventionally activated and produced by two methods: (1) batch method and (2) continuous method. That is, as shown in FIG. 3, raw material 20 such as cloth, non-woven fabric and felt is kept in a high temperature furnace 21, and a gas such as water or carbon dioxide gas is supplied from an activating gas supply hole 23 in an inert atmosphere 22. Is the batch method. Reference numeral 24 is an activating gas tank, and 25 is a furnace temperature control device. The heater is omitted in this figure. Further, as shown in FIG. 4, the raw material 30 such as cloth, non-woven fabric and felt is continuously fed from the inlet 32 of the furnace 31, the activation gas is supplied from the activation gas supply hole 33 to activate the raw material, and the outlet of the furnace is supplied. The continuous method is a method for continuously obtaining the activated carbon fiber constituent obtained from 34. Reference numeral 35 is an activating gas tank, 36 is a heater for heating a furnace, 37 is a feeding device for the raw material 30, and 38 is a product winding device.
このようにして得られた活性炭繊維布などは、片面にア
ルミニウムなどの集電体層を形成し、円形に打抜いて、
セパレータを介して対向させ、第５図のように組立てて
電気二重層キャパシタとする。図中40,41は活性炭繊
維、42,43はアルミニウム集電体、45はセパレータ、46
はケース、47は蓋、48はガスケットであり、コイン型に
構成される。活性炭繊維40,41には電解液が含浸され、
活性炭と電解液との界面の電気二重層により、外径11m
m、厚さ2.0mmの寸法で2Fの大容量を蓄積することが可能
になる。The activated carbon fiber cloth and the like thus obtained has a current collector layer such as aluminum formed on one side and is punched into a circle,
The electric double layer capacitors are assembled by facing each other with a separator interposed therebetween as shown in FIG. In the figure, 40 and 41 are activated carbon fibers, 42 and 43 are aluminum current collectors, 45 is a separator, 46
Is a case, 47 is a lid, and 48 is a gasket, and is configured in a coin shape. The activated carbon fibers 40, 41 are impregnated with an electrolytic solution,
An outer diameter of 11 m due to the electric double layer at the interface between activated carbon and electrolyte
With a size of m and a thickness of 2.0 mm, it is possible to store a large capacity of 2F.
発明が解決しようとする問題点 上記のバッチ法は、高温賦活をバッチ処理で行なうた
め、炉の昇温，降温に非常に長時間を要し、これに伴な
うエネルギ消費も大きくなり、生産性，コストの点で不
利になる。得られた活性炭繊維の特性（比表面積，細孔
分布）や、これを分極性電極として用いた電気二重層キ
ャパシタの特性も、後述するように改善の余地がある。Problems to be Solved by the Invention In the batch method described above, since high temperature activation is performed by batch processing, it takes a very long time to raise and lower the temperature of the furnace, resulting in a large energy consumption and It is disadvantageous in terms of performance and cost. The properties (specific surface area, pore distribution) of the obtained activated carbon fiber and the properties of the electric double layer capacitor using the activated carbon fiber as a polarizable electrode also have room for improvement as described later.
一方、連続賦活法は、高温炉中に連続的に原料を投入す
ることにより活性炭繊維を連続的に得ることができ、エ
ネルギコスト，生産性の点では非常に優れたものにな
る。特に連続布，ロングフィラメント束のような連続体
を賦活する時は非常に有利になる。活性炭の特性の点で
も、原料と賦活ガスの接触反応機会がバッチ賦活の時よ
りも大きく大比表面積の活性炭繊維が得られ、これを用
いたキャパシタの特性も優れる。On the other hand, in the continuous activation method, activated carbon fibers can be continuously obtained by continuously charging raw materials into a high-temperature furnace, which is extremely excellent in terms of energy cost and productivity. This is especially advantageous when activating continuous bodies such as continuous cloths and long filament bundles. Also in terms of the characteristics of activated carbon, the chance of contact reaction between the raw material and the activated gas is larger than in the case of batch activation, and activated carbon fibers having a large specific surface area are obtained, and the characteristics of the capacitor using the same are excellent.
ところで、活性炭は、大比表面積の表面吸着が大きな特
徴であり、賦活過程の最終段階にどのような雰囲気に置
かれていたがその吸着特性を大きく支配する。この点、
従来の賦活法では賦活過程において比較的温度の低い水
蒸気ガスにさらされる可能性があり、第４図に示すよう
な連続賦活法では低温水蒸気に接触して賦活反応が終了
することになり、これを電極に用いたキャパシタは特に
その低温特性が劣る。By the way, activated carbon has a large characteristic of surface adsorption with a large specific surface area, and the adsorption property largely governs the atmosphere in which it was placed in the final stage of the activation process. In this respect,
In the conventional activation method, there is a possibility of being exposed to steam gas having a relatively low temperature in the activation process, and in the continuous activation method as shown in Fig. 4, the activation reaction ends by contact with low temperature steam. Especially, the low temperature characteristics of the capacitor using the electrode are inferior.
問題点を解決するための手段 本発明は、賦活工程とこれに続く熱処理工程とを連続し
て行なうことができるように構成された賦活炉であり、
被賦活物を炭化賦活し、引続きこれを熱処理することを
特徴とする。Means for Solving the Problems The present invention is an activation furnace configured to be able to continuously perform an activation step and a subsequent heat treatment step,
It is characterized in that the material to be activated is activated by carbonization, and subsequently this is heat-treated.
作 用 本発明によれば、連続賦活の最終段階において被賦活物
を熱処理する工程を経るため、比表面積の大きな、また
キャパシタ特性に有利な細孔分布を有する活性炭繊維を
連続的に得ることができる。According to the present invention, the activated carbon fiber having a large specific surface area and a pore distribution advantageous for capacitor characteristics can be continuously obtained since the activated material is subjected to a heat treatment step in the final stage of continuous activation. it can.
さらに、この賦活炉，賦活方法を用いると、得られる活
性炭の特性ばらつきが小さくなり、これを電極に用いた
キャパシタは大容量で安定な低温特性を有する。Furthermore, when this activation furnace and activation method are used, variations in the characteristics of the activated carbon obtained can be reduced, and a capacitor using this as an electrode has a large capacity and stable low temperature characteristics.
賦活ガスとしては、水蒸気，炭酸ガス，炭化水素ガスの
単独又はこれらと不活性ガスとの混合物が用いられる。As the activating gas, water vapor, carbon dioxide gas, hydrocarbon gas, or a mixture of these with an inert gas is used.
実施例 第１図，第２図が本発明の賦活炉の基本的な構成であ
る。第１図のものは縦型炉であり、マッフル１上部の入
口２、下部の出口３、加熱用ヒータ4,5、賦活ガス供給
孔６から基本的に構成され、原料繊維は上部入口２から
炉中に入れられマッフル１中のＡ部、即ち賦活ガス供給
孔６より上方の部分に賦活ガスが供給されるので、ここ
で炭化賦活され、同じくＢ部で熱処理される。ヒータ4,
5は適切に温度設定調節し、炭化賦活、熱処理できる。
炉下部出口３からは窒素ガスのような不活性ガスを供給
する。Example FIG. 1 and FIG. 2 show the basic constitution of the activation furnace of the present invention. FIG. 1 shows a vertical furnace, which is basically composed of an inlet 2 at the upper part of the muffle 1, an outlet 3 at the lower part, heaters 4,5 for heating, and an activating gas supply hole 6, and raw material fibers from the upper inlet 2 Since the activation gas is supplied to the A portion of the muffle 1 in the furnace, that is, the portion above the activation gas supply hole 6, the activation gas is carbonized and activated at the B portion. Heater 4,
5 can be appropriately temperature-set, carbonized and heat treated.
An inert gas such as nitrogen gas is supplied from the furnace lower outlet 3.
第２図は横型炉であり、マッフル10の左右に開口部11,1
2を有し、マッフル途中に賦活ガス供給孔13を有する。1
4,15は加熱用ヒータである。原料16を開口部11から横方
向にマッフル中に入れ、他方の開口部12から不活性ガス
を供給すると、賦活ガス供給孔13より開口部11までのゾ
ーン17は賦活ガス雰囲気となるので炭化賦活が進行する
部分になり、賦活ガス供給孔13より開口部12までのゾー
ン18は熱処理ゾーンとなる。Figure 2 shows a horizontal furnace with openings 11,1 on the left and right of the muffle 10.
2 and an activation gas supply hole 13 in the middle of the muffle. 1
4, 15 are heaters for heating. When the raw material 16 is put into the muffle in the lateral direction from the opening 11 and the inert gas is supplied from the other opening 12, the zone 17 from the activating gas supply hole 13 to the opening 11 becomes an activating gas atmosphere, and thus carbonization is activated. Zone 18 from the activation gas supply hole 13 to the opening 12 becomes a heat treatment zone.
次に本発明の具体的な実施例について述べる。Next, specific examples of the present invention will be described.
実施例１ 目付250g/m2のフェノール樹脂系ノボラック繊維布を第
１図の縦型炉を用いて炭化賦活する。得られた活性炭繊
維布の片面に厚さ300μｍのアルミニウム層をプラズマ
溶射法により形成する。これを直径5mmの円形に打抜
き、第５図のような構成のキャパシタを組立てる。Example 1 A phenol resin type novolac fiber cloth having a basis weight of 250 g / m 2 is activated by carbonization using the vertical furnace shown in FIG. An aluminum layer having a thickness of 300 μm is formed on one surface of the obtained activated carbon fiber cloth by a plasma spraying method. This is punched out into a circle with a diameter of 5 mm, and a capacitor having the structure shown in FIG. 5 is assembled.
実施例２ 目付250g/m2のフェノール樹脂系ノボラック繊維布を第
２図の横型炉を用いて炭化賦活する。得られた活性炭繊
維布の片面にアルミニウム層（厚さ300μｍ）を形成
し、これを直径5mmの円形に打抜く。これを正極とし、
負極には直径5mmの円形のLiドープSn−Pb合金を用い、
第５図と同じような構成（負極のみが異なる）のエネル
ギ貯蔵装置を組立てる。Example 2 A phenol resin-based novolac fiber cloth having a basis weight of 250 g / m 2 is activated by carbonization using the horizontal furnace shown in FIG. An aluminum layer (thickness: 300 μm) is formed on one side of the obtained activated carbon fiber cloth, and this is punched into a circle having a diameter of 5 mm. This is the positive electrode,
Using a circular Li-doped Sn-Pb alloy with a diameter of 5 mm for the negative electrode,
An energy storage device having the same configuration as that of FIG. 5 (only the negative electrode is different) is assembled.
比較例１ 原料布およびキャパシタ構成は実施例１と同じで、布の
炭化賦活を第３図のバッチ炉で行なう。Comparative Example 1 The composition of the raw material cloth and the capacitor is the same as in Example 1, and the carbonization of the cloth is carried out in the batch furnace shown in FIG.
比較例２ 原料布およびキャパシタ構成は実施例１と同じで、布の
炭化賦活を第４図の従来連続炉で行なう。Comparative Example 2 The composition of the raw material cloth and the capacitor is the same as in Example 1, and the carbonization activation of the cloth is performed in the conventional continuous furnace of FIG.
次表に得られた活性炭繊維の特性およびキャパシタ特性
を列挙する。The following table lists the characteristics of the obtained activated carbon fiber and the characteristics of the capacitor.
以上の実施例では、布を原料に用いた例についてのみ述
べたが、連続ロングフィラメント状トウ繊維を同じよう
に賦活してチョップ状に切断し、パルプ，セラミック繊
維のような補強材繊維と混合して紙状に抄造し、これを
電極に用いても同じような効果が得られる。 In the above examples, only the case where the cloth is used as the raw material is described, but the continuous long filament tow fibers are similarly activated and cut into chops, and mixed with the reinforcing fibers such as pulp and ceramic fibers. Then, the same effect can be obtained by making a paper-like paper and using this as an electrode.
また第１図，第２図の賦活炉の出口孔3,12の部分に室温
不活性ガス雰囲気室を設け、得られた活性炭繊維を収納
すると操作上有利である。Further, it is advantageous in operation that a room temperature inert gas atmosphere chamber is provided in the outlet holes 3 and 12 of the activation furnace shown in FIGS. 1 and 2 and the activated carbon fiber obtained is stored therein.
以上の実施例では、被賦活物として未炭化のものを用
い、本発明炉を用いて一度に炭化賦活熱処理する方法に
ついて述べたが、予め炭化したものを本発明の賦活炉を
用いて賦活熱処理を行なうこともできる。In the above examples, an uncarbonized material was used as the activated material, and a method of performing carbonization activation heat treatment at once using the furnace of the present invention was described, but previously carbonized one was activated heat treatment using the activation furnace of the present invention. You can also do
発明の効果 以上のように、本発明によれば、安定した特性の大比表
面積の活性炭繊維が連続的に得られ、活性炭の特性，生
産性いずれの点でも優れる。また、この活性炭を電極に
用いた電気二重層キャパシタの特性も、従来のバッチ
炉，連続炉で得られた活性炭を用いたものよりも優れ
る。EFFECTS OF THE INVENTION As described above, according to the present invention, activated carbon fibers having a large specific surface area with stable characteristics are continuously obtained, and the characteristics and productivity of activated carbon are excellent. Further, the characteristics of the electric double layer capacitor using this activated carbon as an electrode are also superior to those using the activated carbon obtained in the conventional batch furnace and continuous furnace.
第１図及び第２図は本発明の賦活炉の基本構成を示す縦
断面図、第３図及び第４図は従来の賦活炉の縦断面図、
第５図は活性炭繊維を分極性電極に用いたキャパシタの
縦断面図である。 1,10……マッフル、2,3,11,12……開口部、4,5,14,15…
…ヒータ、6,13……賦活ガス供給孔。1 and 2 are vertical cross-sectional views showing the basic structure of an activation furnace of the present invention, and FIGS. 3 and 4 are vertical cross-sectional views of a conventional activation furnace.
FIG. 5 is a vertical cross-sectional view of a capacitor using activated carbon fiber as a polarizable electrode. 1,10 …… Muffle, 2,3,11,12 …… Opening, 4,5,14,15…
… Heater, 6,13 …… Activating gas supply hole.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−173118（ＪＰ，Ａ) 特開 昭53−31820（ＪＰ，Ａ) 特開 昭58−69709（ＪＰ，Ａ) 特開 昭59−217612（ＪＰ，Ａ) 特許138698（ＪＰ，Ｃ１) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-173118 (JP, A) JP-A-53-31820 (JP, A) JP-A-58-69709 (JP, A) JP-A-59- 217612 (JP, A) Patent 138698 (JP, C1)
Claims (3)
し、一方の開孔部から被賦活物を連続的に投入し、他方
の開孔部から賦活物を取り出す賦活炉において、炉室の
途中から賦活ガスを供給し、被賦活物の入口側へ賦活ガ
スを導くように構成し、被賦活物の入口に近い炉室部で
賦活を行い、引続き連続的に出口に近い炉室部で不活性
ガス雰囲気で熱処理を行うことを特徴とする賦活炉。1. An activation furnace which has openings in the upper and lower parts or left and right parts of a furnace chamber, into which an activator is continuously charged from one opening and which is taken out from the other opening. , The activation gas is supplied from the middle of the furnace chamber, and the activation gas is guided to the inlet side of the activated material, and the activation is performed in the furnace chamber portion close to the inlet of the activated material, and continuously close to the outlet. An activation furnace characterized by performing heat treatment in an inert gas atmosphere in a furnace chamber.
る織布，不織布，糸，トウ状物，フェルト，紐のうちの
いずれかであることを特徴とする特許請求の範囲第１項
記載の賦活炉。2. The activated material is any one of a continuous fiber or a woven fabric, a non-woven fabric, a thread, a tow-like material, a felt, and a string made of the fiber, according to claim 1. Activation furnace.
物を炭化賦活雰囲気から外に出すことなく、引続き熱処
理することを特徴とする賦活方法。3. A method of activation, which comprises activating carbonization of a material to be activated, and subsequently subjecting the obtained carbonization activation material to heat treatment without being taken out from a carbonization activation atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60296730A JPH0674124B2 (en) | 1985-12-27 | 1985-12-27 | Activation furnace and activation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60296730A JPH0674124B2 (en) | 1985-12-27 | 1985-12-27 | Activation furnace and activation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62158108A JPS62158108A (en) | 1987-07-14 |
| JPH0674124B2 true JPH0674124B2 (en) | 1994-09-21 |
Family
ID=17837350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60296730A Expired - Lifetime JPH0674124B2 (en) | 1985-12-27 | 1985-12-27 | Activation furnace and activation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674124B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819363B (en) * | 2019-10-24 | 2021-06-01 | 东南大学 | Multi-cavity series self-heating external heating converter biomass carbonization-activation device and method |
| JP7557410B2 (en) * | 2021-03-31 | 2024-09-27 | 日本製紙株式会社 | Activated carbon fiber material and its manufacturing method |
| CN113149009A (en) * | 2021-05-06 | 2021-07-23 | 国家能源集团宁夏煤业有限责任公司 | Automatic feeding device and method for activated carbon activation furnace |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5825043B2 (en) * | 1976-09-03 | 1983-05-25 | 東邦ベスロン株式会社 | Continuous production method of fibrous activated carbon |
| JPS5869709A (en) * | 1981-10-08 | 1983-04-26 | デグ−サ・アクチエンゲゼルシヤフト | Method and apparatus for activating and reactivating particularly active carbon for carrying out gas/solid reaction |
| JPS59217612A (en) * | 1983-05-24 | 1984-12-07 | Keihan Rentan Kogyo Kk | Apparatus for producing activated carbon |
| JPS60173118A (en) * | 1984-02-17 | 1985-09-06 | Nippon Soken Inc | Activation treatment and device of carbon yarn therefor |
-
1985
- 1985-12-27 JP JP60296730A patent/JPH0674124B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62158108A (en) | 1987-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4064207A (en) | Fibrillar carbon fuel cell electrode substrates and method of manufacture | |
| DE69903405T2 (en) | MATERIAL FOR ELECTRODE | |
| CN101380535B (en) | Multiple layer composite micropore filtration separation material and preparation method and use thereof | |
| EP0162976B1 (en) | Process for preparation of porous carbon plates | |
| EP0473715A4 (en) | Mixed fiber composite structures: method of preparation, articles therefrom, and uses therefor | |
| DE20022262U1 (en) | Electrode substrate for electrochemical cells | |
| EP0134706B1 (en) | Electric double layer capacitor and method for producing the same | |
| US20050260909A1 (en) | Carbonic fiber woven fabric, carbonic fiber woven fabric roll, gas diffusion layer material for solid polymer fuel cell, method for producing carbonic fiber woven fabric and method for producing gas diffusion layer material for solid polymer fuel cell | |
| CN101380536B (en) | Multiple layer composite micropore filtration separation material and preparation method and use thereof | |
| WO2020184451A1 (en) | Carbon electrode material for manganese/titanium-based redox flow battery | |
| JPH0674124B2 (en) | Activation furnace and activation method | |
| JP7388361B2 (en) | Carbon electrode materials and redox batteries | |
| JPS59144625A (en) | Manufacturing method of carbon fiber sheet | |
| US20050233200A1 (en) | Process to manufacture an ion-permeable and electrically conducting flat material, the material obtained according to the process, and fuel cells | |
| JPS628448A (en) | Manufacturing method of activated carbon for polarizable electrodes | |
| JPH0660884A (en) | Manufacture of porous carbon sheet for phosphoric acid fuel cell | |
| JPS61119716A (en) | Carbon fiber having large surface area, production thereof, and catalyst carrier made of said carbon fiber | |
| JPH05239720A (en) | Metal-halogen secondary battery electrode materials and electrodes | |
| JPH034508B2 (en) | ||
| CN211665430U (en) | Active carbon fiber felt for hydrogen storage | |
| JP2004084136A (en) | Method for producing carbonaceous fiber woven fabric, carbonaceous fiber woven fabric, and gas diffusion layer material for polymer electrolyte fuel cell | |
| JP7554175B2 (en) | Anode gas diffusion layer substrate | |
| JPH03285873A (en) | Carbon plate and production thereof | |
| JPH0859360A (en) | Method for manufacturing porous carbon material | |
| JPH07220732A (en) | Method for producing porous carbon plate for phosphoric acid fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |